Alloying Confined Regulation of Nanoparticles in aHierarchically Directed Porous Carbon for Zinc–Air Batteries

The rational design of non-noble metal-based electrocatalysts with efficient bifunctional catalytic activity is critical for the widespread application of zinc–air batteries (ZABs). In this study, an FeNi alloy encapsulated three-dimensional honeycomb-like network structure of carbon aerogels (FeNi/CAs) electrocatalyst was constructed using directional freeze-drying technology. The innovative architecture, combined with the synergistic effect between Fe and Ni, endows the FeNi/CAs catalyst with outstanding bifunctional catalytic activity compared with the introduction of a single metal in carbon aerogels. Specifically, the catalyst achieves a high half-wave potential (<i>E</i>_1/2) of 0.90 V for the oxygen reduction reaction (ORR) and excellent stability with a negligible shift of <i>E</i>_1/2 (9 mV) after 2000 cycles. Moreover, the FeNi/CAs catalyst exhibits a smaller potential difference (Δ<i>E</i> = 0.68 V) between the ORR and oxygen evolution reaction (OER), highlighting its superior bifunctional activity. Furthermore, the rechargeable ZABs with FeNi/CAs catalysts show remarkable power density (226 mW cm^–2) and energy density (985 mWh kg^–1), as well as over 1200 h of cycling stability. Additionally, the discharge rate performance of the assembled flexible all-solid-state battery based on this catalyst remains stable under different bending angles, suggesting its robustness and potential for use in wearable electronic devices. This work provides a compelling strategy for the construction of advanced electrocatalysts by leveraging hierarchical structural features and metal synergy, paving the way for high-performance and durable ZABs in next-generation energy storage applications.